JPH0732751A - Oxalyl amino-substituted indoaniline dye for dye sublimable thermal transfer printing - Google Patents

Abstract

PURPOSE: To obtain a dye having high solubility in an ecologically allowable solvent and a low melting point by using a dye expressed by a specified formula in a dye-donor for dye thermal sublimation transfer which comprises a support provided with a dye layer containing a dye and a polymer binder. CONSTITUTION: In a dye-donor for a dye thermal sublimation transfer method which comprises a support provided with a dye layer containing a dye and a polymer binder, a dye shown by a general formula shown separately is used. In the formula, R<1> -R<3> are each hydrogen, halogen, nitro, alkyl, or the like; R<4> is OR<5> , SR<5> , NR<5> R<6> or a heterocyclic group (R<5> , R<6> are each hydrogen, alkyl, allyl, or the like); R<7> , R<8> are each hydrogen, alkyl, aryl, or a heterocyclic group; R<9> -R<12> are each hydrogen, hydroxyl, halogen, alkyl, or the like. The dye layer of the dye-donor is arranged to face the dye image accepting layer of an accepting sheet and heated in the image forming direction to form an image.

Description

Detailed Description of the Invention

[0001]

This invention relates to a dye sublimation thermal transfer method (th
The present invention relates to a dye-donor element used for ermal dye sublimation transfer) and a novel dye used for the dye-donor element.

[0002]

2. Description of the Related Art The dye sublimation thermal transfer method is the following recording method. That is, a dye-donor element provided with a dye layer containing a sublimable dye having thermal transfer property is used as a receiver sheet.
sheet) or a receiving element, and then selectively heated by a thermal printing head with a plurality of parallel heating resistors according to a pattern information signal so that the dye is removed from the selectively heated area of the dye-donor element. It is a recording method which is transferred to a receiving sheet to form a pattern on the sheet, and the form and density of the pattern are determined by the heat pattern and intensity applied to the heat donating material.

Dye-donor elements used in dye sublimation thermal transfer processes usually consist of a very thin support, such as a polyester support, one side of which is coated with a dye layer of printing dye. Usually, an adhesive layer or a subbing layer is provided between the support and the dye layer. The opposite surface is usually coated with a sliding layer that provides a lubricious surface through which the thermal print head can pass without wear. The adhesive layer is provided between the support and the sliding layer.

The dye layer may be a monochromatic dye layer or may be composed of regions in which dyes of various colors, for example cyan, magenta and optionally black, are repeated in sequence.
When a dye-donor element containing three or more primary color dyes is used, a multicolor image can be obtained by sequentially performing the steps of the dye transfer process for each color.

A primary dye layer, for example a magenta or cyan or yellow dye layer, may contain only one primary dye (magenta or yellow dye respectively) or two or more of the same hue. It may contain a mixture of primary color dyes (2 magenta, 2 cyan or 2 yellow dyes respectively).

Any dye can be used in the dye layer provided it is readily transferable to the dye-image-receiving layer of the receiving sheet or material by the action of heat.

Typical examples of dyes used in the dye sublimation thermal transfer method are described in the following patent documents, for example. That is, EP209990, EP209991,
EP216484, EP218397, EP22709
5, EP227096, EP229374, EP235
939, EP247737, EP257575, EP2
57580, EP258856, EP279330, E
P279467 and EP285665; US4743
582, US4753922, US4753923, U
S4757046, US4769360, US4771
035 and US 5026677; and JP84 /
78894, JP84 / 78895, JP84 / 788
96, JP84 / 227490, JP84 / 22794
8, JP85 / 27594, JP85 / 30391, J
P85 / 229787, JP85 / 229789, JP
85/229790, JP85 / 229791, JP8
5/229792, JP85 / 229793, JP85
/ 229795, JP86 / 41596, JP86 / 2
68493, JP86 / 268494, JP86 / 26
8495 and JP86 / 284489.

Despite the large number of existing dyes, new dyes and especially dyes suitable for use in dye-donor materials for dye sublimation thermal transfer printing processes, preferably low melting point and ecologically acceptable solvents Research into dyes that have excellent solubility in water is still ongoing.

[0009]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide new dye-donor elements for use in dye sublimation thermal transfer printing processes.

Another object of the present invention is to provide a novel dye which can be used in the dye-donor element.

Another object of the present invention is to provide a novel dye having a high solubility in an ecologically acceptable solvent and a low melting point. Other objects of the present invention will be apparent from the following description.

[0012]

According to the present invention there is provided a dye-donor element for use in a dye sublimation thermal transfer process, said dye-donor element comprising a support comprising a dye layer containing a dye and a polymeric binder. The dye is represented by the following formula (I):

[Chemical 2] [Wherein R ¹ , R ² and R ³ are each independently hydrogen,
Halogen, nitro, alkyl group, cycloalkyl group, aryl group, allyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, amino group, CN, carboalkoxy group, sulfonylamino group or carbonamido group ( carbonamido grou
p), any of these groups may be substituted, or R ² and R ³ represent the atoms necessary to form a ring with the atoms to which they are attached; R ⁴ is O
R ⁵ , SR ⁵ , NR ⁵ R ⁶ or a heterocyclic ring (in the formula, R ⁵ and R ⁶ are each independently hydrogen, an alkyl group, an allyl group, an aryl group, a cycloalkyl group, an alkenyl group or a heterocyclic ring). Represents a ring ring, or R ⁵ and R ⁶
Represents the atoms necessary to form a heterocyclic ring with the atoms to which they are attached; R ⁷ and R ⁸ each independently represent hydrogen, an alkyl group, an aryl group or a heterocyclic group, or R ⁷ and R ⁸ represent the atoms necessary to form a heterocyclic ring with the atoms to which they are attached, or R ⁷ or R ⁸ and R ⁹ or R ¹² are rings with the atoms to which they are attached. represents the atoms necessary to form a; each R ^9, R ^10, R ¹¹ and R ^12, are independently hydrogen, hydroxy, halogen, alkyl group, cycloalkyl group, an aryl group, an amino group, an alkyloxy group , an aryloxy group, a carbamoyl group, a sulfamoyl ^{_{group, NH-SO 2 R 13,}} NH-COR 13, O
Represents —SO ₂ R ¹³ or O—COR ¹³ , or R ⁹
And R ¹⁰ or R ¹¹ and R ¹² represent an atom necessary for forming a ring together with the atom to which they are connected (in the formula, R ¹³ is an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group). Group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group or a heterocyclic group)]].

The present invention provides a novel dye represented by the above formula (I).

According to the invention, the dye layers of said dye-donor element are further arranged in face-to-face relationship with the dye image-receiving layer of the receiving sheet; the combination thus obtained is imaged in the imaging direction. Image-wise heating
); And then separating the receiver sheet from the dye-donor element; a step of forming an image by the dye sublimation thermal transfer process is provided.

Preferably, R ¹ represents hydrogen; R ² represents hydrogen or acylamino, alkoxy, alkyl group, alkylthio group, alkylcarbonamido group or dialkylamino group; R ³ represents hydrogen or halogen; R ⁴ Represents an alkoxy group, an alkylthio group, a dialkylamino group, a monoalkylamino group, an aryloxy group, an arylthio group, or a heterocyclic group such as piperidyl, pyrrolidinyl, morpholinyl, furyl or thienyl; R ⁷ and R ⁸ both represent an alkyl group. Represents; R ⁹ represents hydrogen; R ¹⁰ represents hydrogen, an alkoxy group,
Represents an amino group or an alkyl group; R ¹¹ represents hydrogen or an alkyl group; and R ¹² represents hydrogen.

Representative examples of novel dyes of formula (I) are listed in Tables 1 and 2 below.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

[0022]

[Table 6]

[0023]

[Table 7]

The dyes according to the present invention can be obtained by oxidative coupling methods known in the art of p-phenylenediamine compounds or p-nitrosoaniline compounds with suitable phenols.

Representative examples of suitable p-phenylenediamine compounds are 4-N, N-dimethylaminoaniline; 4
-N, N-diethylaminoaniline; 4- (N-ethyl, N-hydroxyethyl) aminoaniline; 4- (N
-Ethyl, N-cyanomethyl) aminoaniline; 4-
(N-ethyl, N-ethylsulfonic acid) aminoaniline; 2-methyl, 4- (N, N-dihydroxyethyl)
Aminoaniline; 2-methyl, 4- (N, N-diethylacetate) aminoaniline; 2,6-dimethyl, 4-
(N, N-dihydroxyethyl) aminoaniline; 2,
3,5,6-tetramethyl-4-N, N-diethylaminoaniline; 4-piperidinoaniline; 4-morpholinoaniline; 4-pyrrolidylaniline; 4-imidazoloaniline.

The dye represented by the above formula (I) exhibits a cyan hue, that is, absorbs in the infrared region. These dyes can be used as cyan color image forming dyes for silver halide color photographic materials by utilizing the above coupling reaction, and these dyes can be used in the process of silver halide color photography by the above coupling reaction. Generate an image according to These dyes are also useful as cyan filter dyes for silver halide color photographic materials and as antihalation dyes. Further, these dyes can be used in inkjet printing after being functionalized with hydrophilic groups. These dyes are also used in resistive ribbon printing.
printing), for example laser-based inks, fabrics, lacquers and paints. These dyes can also be used in transfer printing on fabrics and construction of filter array elements.

According to a preferred embodiment of the present invention, these dyes can be used as a cyan dye or an IR dye in the dye layer of the dye-donor element for dye sublimation thermal transfer process.

Further, these dyes have an absorption maximum wavelength of 70.
When it exceeds 0 nm, it can also be used as an IR absorbing dye in the dye layer of the dye-donor element for laser-induced thermal transfer.

The dye layer of the dye-donor element of the invention is preferably prepared as follows. That is, a dye, a polymeric binder medium, and other optional components are added to a suitable solvent or solvent mixture, and these components are dissolved or dispersed to prepare a coating composition, and the composition is previously prepared with an adhesive layer. Alternatively, it is produced by applying an undercoat layer on a support provided with the undercoat layer and then drying.

The dye layer thus produced generally has a thickness of about 0.2 to 5.0 μm, preferably 0.4 to 5.0 μm.
2.0 μm, and the dye: binder weight ratio is generally 9: 1 to 1.3, preferably 2: 1 to 1: 2.

The following can be used as the polymer binder. That is, a cellulose derivative such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxycellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose nitrate, cellulose acetate formate, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, acetic acid. Cellulose pentanate,
Cellulose acetate benzoate, cellulose triacetate; Vinyl resins and derivatives such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, copolyvinyl butyral-vinyl acetal-vinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetoacetal, polyacrylamide; acrylate and acrylate derivatives Polymers and copolymers of eg polyacrylic acid,
Polymethylmethacrylate and styrene-acrylate copolymers; polyester resins; polycarbonates; copolystyrene-acrylonitrile; polysulfones; polyphenylene oxides; organosilicones such as polysiloxanes; epoxy resins; and natural resins such as arabic rubber. The binder for the dye layer of the present invention is preferably composed of cellulose acetate butyrate or copolystyrene-acrylonitrile.

The dye of the present invention can be used as a mixture with other known dyes for thermal sublimation printing. In particular the dyes of the invention are EP92203566 and EP922032.
No. 08, the tricyanovinyl dyes and dicyanovinyl dyes, and the malononitrile dimer-derived dyes described in EP-A-400706 can be used in combination. Further, the dye of the present invention can be used as a mixture with an azo dye such as a disperse azo dye, an anthraquinone dye, an indoaniline dye and an azomethine dye. Examples of dyes that can be used in combination with the dye of the present invention are disclosed in, for example, the following patent documents. That is, EP92203
979, EP209990, EP209991, EP2
16483, EP218397, EP227095, E
P227096, EP229374, EP23593
9, EP247737, EP257575, EP257
580, EP258856, EP279330, EP2
79467 and EP285665; US474358.
2, US4753922, US4753923, US4
757046, US4769360, US477103
5 and US 5026677; JP 84/78894,
JP84 / 78895, JP84 / 78896, JP8
4/227490, JP84 / 227948, JP85
/ 27594, JP85 / 30391, JP85 / 22
9787, JP85 / 229789, JP85 / 229
790, JP85 / 229791, JP85 / 2297
92, JP85 / 229793, JP85 / 22979
5, JP86 / 41596, JP86 / 268493,
JP86 / 268494, JP86 / 268495 and JP86 / 284489; and US483933.
6, US5168094, US5147844, US5
177052, US5175069, US515508
8, US5166124, US5166129, US5
166128, US5134115, US513227
6, US 5132275, US 5132274, US5
132273, US5132268, US513226
7, US5126314, US5126313, US5
126312, US5126311, US5131341
6, US4975410, US4885272 and U
For example, S4886029.

Further, the coating layer may contain other additives such as a curing agent, a preservative, organic or inorganic fine particles, a dispersant, an antistatic agent, a defoaming agent and a viscosity control agent. These and other ingredients are described in EP133011,
EP133012, EP111004 and EP279
467 is more fully described.

Dimensionally stable, capable of withstanding relevant temperatures up to 400 ° C. for times up to 20 msec, yet thin enough to transfer the heat applied to one side to the dye on the other side, Generally 1-10ms within the above short time
Any material can be used as a support for the dye-donor element provided that transfer is made to the receiving sheet during ec. Such materials include polyesters such as polyethylene terephthalate, polyamides, polyacrylates, polycarbonates, cellulose esters, fluorinated polymers, polyethers, polyacetals, polyolefins, polyimides, glassine paper and There is condenser paper. A support made of polyethylene terephthalate is preferred. Generally, the support has a thickness of 2-3.
It is 0 μm. The support may be coated with an adhesive layer or a subbing layer, if desired.

The dye layer of the dye-donor element may be coated on the support or printed on the support by printing techniques such as gravure.

A dye barrier layer comprising a hydrophilic polymer is also used between the support and the dye layer of the dye-donor element to prevent the dye from erroneously transferring back to the support. The transfer density can be increased. The dye barrier layer contains a hydrophilic material useful for this purpose. In general, excellent results have been obtained with the following substances. That is, gelatin, polyacrylamide, polyisopropylacrylamide, butyl methacrylate-grafted gelatin, ethyl methacrylate-grafted gelatin, ethyl acrylate-grafted gelatin, cellulose monoacetate, methyl cellulose, polyvinyl alcohol, polyethyleneimine, polyacrylic acid, polyvinyl alcohol and It is a mixture of polyvinyl acetate, a mixture of polyvinyl alcohol and polyacrylic acid, or a mixture of cellulose monoacetate and polyacrylic acid. Suitable dye barrier layers are eg EP227091 and EP228.
065. Certain hydrophilic polymers, such as those described in EP 227091, also have suitable adhesion to the support and dye layers, eliminating the need for a separate adhesive or subbing layer. Therefore, these particular hydrophilic polymers used in a single layer in the dye-donor element perform two functions and are therefore referred to as dye barrier / subbing layers.

The opposite side of the dye-donor element is preferably coated with a slip layer to prevent the printhead from sticking to the dye-donor element. Such a slipping layer consists of a surfactant, a liquid lubricant, a solid lubricant or a mixture thereof, and may or may not contain a polymer binder. These surfactants are agents known in the art, such as carboxylates, sulfonates,
Phosphonates, aliphatic amine salts, aliphatic quaternary ammonium salts, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, fluoroalkyl C ₂ -C ₂₀ fatty acids. Examples of liquid lubricants are silicone oils, synthetic oils, saturated hydrocarbons and glycols. Examples of solid lubricants include:
Examples include various higher alcohols such as stearyl alcohol, fatty acids and fatty acid esters. Suitable sliding layers are described, for example, in EP 138483 and EP 227090 and US 4567113, US4.
572860 and US4717711.

Supports for receiving sheets used with dye-donor elements are, for example, polyethylene terephthalate, polyether sulfones, polyimides, cellulose esters or polyvinyl alcohol-co-acetals (polyvi).
It is a transparent film of nyl alcohol-co-acetal). The support may also be reflective, such as barita-coated paper, polyethylene-coated paper, or white polyester or polyester with white pigments added.

In order to avoid improper adsorption of the transferred dye to the support of the receiving sheet, this support is coated with a specific surface dye image-receiving layer, ie a layer in which the dye can diffuse more easily. There must be. The dye image receiving layer may be, for example, polycarbonate, polyurethane, polyester, polyamide, polyvinyl chloride, polystyrene-co-
It is composed of acrylonitrile, polycaprolactone or a mixture thereof. The dye image-receiving layer is also composed of a thermoset product of poly (vinyl chloride-co-vinyl acetate-co-vinyl alcohol). Suitable dye receiving layers include, for example, EP133011, EP133012,
EP 144247, EP 227094 and EP 228
066.

In order to improve the light fastness and the stability of the recorded image, a singlet oxygen quencher such as a UV absorber, a HALS compound (Hindered Amine Light Stabilizer), Metal complexes of dyes such as Ni or Cs complexes and / or antioxidants are added to the receiving layer.

The dye layer of the dye-donor element or the dye image-receiving layer of the receiver sheet may also contain a release agent that aids in separating the dye-receiving element from the dye-receiving element after transfer. Also, such release agents can be applied as a separate layer to at least a portion of the dye layer or the receiving layer. Solid waxes, fluorine- or phosphate-containing surfactants and silicone oils are used as release agents. See EP 133 for suitable release agents.
012, JP85 / 19138 and EP227092
It is described in.

The dye-donor element of the invention is used to form a dye transfer image. This process consists of placing the donor element in face-to-face relationship with the dye-receiving layer of a receiver sheet and then subjecting the combination thus obtained, preferably to heating from the back side of the donor element in the imaging direction. Is. Dye transfer is accomplished by heating at a temperature of, for example, 400 ° C. for a few msec, typically 10 ms to 40 ms.

If the process is carried out with only a single color, then a monochrome cyan dye transfer image is obtained, which image is composed of at least one dye of the invention. Multicolor images use donor materials containing three or more primary dyes (one of these dyes is composed of at least one cyan dye of the invention), then the steps of the above process for each color are performed. It can be obtained by carrying out in order. After the first dye is transferred, the donor element is stripped off. The second dye-donor element (or other area of the donor element with other dye areas) is then brought into register with the dye-receiving element for precise overlay and the process is repeated. The third color and optionally more colors are obtained in the same manner.

In addition to the thermal head, laser light, infrared flash or a heated pen can be used as the heat source to supply the thermal energy. Thermal printing heads that can be used to transfer dye from the dye-donor elements of the invention to a receiving sheet are commercially available. When laser light is used (ie what is known as laser induced thermal transfer), the dye layer, or other layer of the dye-donor element, is a compound that absorbs the light emitted by the laser and converts it into heat, such as the invention. Must contain an IR absorbing dye of

Alternatively, the support of the dye-donor element may be an electrically resistive ribbon composed of, for example, a multilayer structure of carbon loaded polycarbonate coated with a thin aluminum coating. Electrically addressing the printhead electrodes and heating the ribbon very locally below the associated electrode causes an electrical current to flow through the electrically resistive ribbon. In this case, heat is generated directly in the resistive ribbon, and therefore it is the ribbon that heats up, which means that the various elements of the thermal head heat up and the head moves to the next print position. There is an inherent advantage in print speed with the resistive ribbon / electrode head method compared to the thermal head method, which must be cooled prior to printing.

The following examples are provided to illustrate the present invention in more detail without limiting its scope of application.

[0047]

Examples Example 1-Synthesis of Dye 1 Dye 1 was prepared according to Reaction Scheme 1.

[0048]

[Chemical 3]

65.4 g of ortho aminophenol (0.
6 mole) was dissolved in 425 ml of acetone. 55.5 g (0.66 mole) of sodium bicarbonate was added. 70.4 ml (0.63 m) of ethyloxalyl chloride was added to the obtained suspension while maintaining the temperature at 40 ° C or lower.
ole) was added dropwise. The reaction mixture obtained was stirred for 1 hour and then poured into 1.5 l of water. The precipitate formed was filtered off, washed with water and dried at 50 ° C. Compound A 113g
(Yield 90%) was obtained. Compound A 20.9 g (0.1
(mole) was dissolved in 800 ml of ethyl acetate and 200 ml of ethanol (solution 1). 22 g (0.11 mole) of 4-diethylamino-aniline hydrochloric acid and 41 g (0.49 mole) of sodium bicarbonate were added to 100 m of water.
It was suspended in 1 and this was added to solution 1. K ₃ Fe
(CN) ₆ 132 g (0.4 mole) of water (400
ml) solution was added to solution 1 and stirring was continued for 1 hour. The organic layer was washed twice with water, dried over sodium sulfate and then concentrated under reduced pressure. The residue was purified by column chromatography (CH ₂ Cl ₂ / EtOAc; 9/1) to obtain 18.5 g (yield 50%) of Dye 1 (melting point: 98 ° C.).

Example 2 All other dyes shown in Tables 1 and 2 were prepared in a similar manner. Non-commercially available oxalyl chloride derivatives can be prepared in situ by methods known to those skilled in the art of organic synthesis. As an example, the production of Dye 4 will be described. Dye 4 was prepared according to Reaction Scheme 2.
Compound C was converted to the corresponding Dye 4 as described in Example 1, Step 2 of Scheme 1.

[0051]

[Chemical 4]

I. BuOH 15.5 ml (0.21 m
ole) was dissolved in 150 ml of dichloromethane and added to a solution of 18.3 ml (0.21 mole) of oxalyl chloride in dichloromethane (100 ml) at -5 ° C over 90 minutes. The resulting solution was stirred at room temperature for 90 minutes. Next, the solution of compound B is added to o-aminophenol 2
1.8 g (0.2 mole) and sodium bicarbonate 35.
3 g (0.42 mole) of dichloromethane (100 m
I) was added to the mixture (20 ° C.). The resulting reaction mixture was stirred at 40 ° C for 1 hour. Dichloromethane was removed under reduced pressure, then the residue was added with 0.5 l of ice water, 5 ml of acetic acid.
And 25 ml of methanol. The precipitate was filtered off, washed with water and methanol and dried to give compound C 4
4.5 g (melting point: 160 ° C., liquefied and solidified again and 2
Decomposes above 30 ° C.).

Example 3-Synthesis of Dye 22 Dye 22 was prepared according to Reaction Scheme 3. Compound D to Dye 22
Is similar to Example 1, Step 2 of Reaction Scheme 1.

[0054]

[Chemical 5]

Compound A 10.5 g (0.05 mol
e) is suspended in 9.0 ml of morpholine and then 45 ° C.
It was heated for 30 minutes. The reaction mixture obtained was treated with 1N
Poured into a mixture of 15 ml of HCl, 25 g of ice and 16 ml of methanol and stirred vigorously for 1 hour. The precipitate was filtered off and washed with water and a methanol / water mixture. Drying gives 11.1 g of compound D (melting point: 125 ° C .;
Liquefy).

Example 4-Synthesis of Dye 25 Dye 25 was prepared using 2- (n-propylamino-oxalylamino) phenol (Compound E). Synthesis of Dye 25 from Compound E is similar to Example 1, Step 2 of Scheme 1. Synthesis of Compound E: 10.5 g of Compound A (0.05 mo
le) is cooled in an ice bath while n-propylamine 2
It was added portionwise to 0 ml (exothermic reaction). The resulting mixture was stirred at 40 ° C. for 1 hour, then 25 g of ice and 1 NH
Poured into a mixture of 50 ml of Cl. Methanol 10
ml was added and the resulting precipitate was stirred for 15 minutes. The precipitate was collected by filtration and washed with water / methanol (1/1). After drying, 10.1 g of compound E was obtained (melting point: 200 ° C .; decomposition).

Example 5 The absorption maximum (λ _max ) and the molar absorption coefficient (ε) of the following dyes were measured in methanol. The measurement results are listed in Table 3.

[0058]

[Table 8]

The dyes of the present invention are compared with the comparative dyes, for example, C1 and dye 2, C2 and dye 30, C3 and dye 2 and C.
It can be seen from Table 3 that the dye 4 and the dye 30 are compared with each other and that they generally absorb long wavelength light and have a high molar extinction coefficient. As a result, the dyes of this invention are more suitable cyan dyes for color printing.

[0060]

[Chemical 6]

Example 6 A dye-donor element used for dye sublimation thermal transfer was prepared as follows. A solution was prepared by dissolving 50 mg of the dye (the nature and amount of which are listed in Table 4 below) and a binder of co-acrylonitrile-styrene in methyl ethyl ketone (10 ml) as a solvent. Wet thickness 100 from this solution
The μm layer was coated on a 5 μm polyethylene terephthalate film. The obtained layer was dried by evaporating the solvent.

The receiving sheet was an undercoated polyethylene terephthalate film having a thickness of 175 μm and 3.6.
g / m ² poly (vinyl chloride / co-vinyl acetate / co-vinyl alcohol) (supplied by Union Carbide
Vinylite VAGD), 0.336 g / cm ² diisocyanate (DESMODURV supplied by Bayer AG)
L), and 0.2 g / m ² of hydroxy-modified polydimethylsiloxane (Tegom supplied by Goldschmidt).
er H SI 2111) prepared by coating a dye image-receiving layer derived from an ethyl methyl ketone solution.

The dye-donor element was printed on a color video printer type CP 100E supplied by Mitsubishi in combination with a receiving sheet as described above.

The receiver sheet is separated from the dye-donor element, and then the maximum color density (D) of the dye image recorded on the receiver sheet.
_max ) was measured with a Macbeth TR 924 densitometer. The test results are listed in Table 4 below.

[0065]

[Table 9]

Example 7 A receiver sheet was prepared as described in Example 6. A black dye-donor element was prepared as follows.
The amount of dye given in Table 5 below was used in each case with 0.5% by weight of poly (styrene-co-acrylonitrile) (German B
It was added to 10 ml of ethyl methyl ketone solution containing Luran 388S) supplied by ASF. The black dye mixture obtained is coated, printed and then used in Example 6 above.
Evaluation was carried out as described in.

The test results are listed in Table 5 below. Prior art dyes C-magenta and C- having the structural formula:
Yellow was used in admixture with the cyan dyes of this invention.

[0068]

[Table 10]

[0069]

[Table 11]

[0070]

[Table 12]

The test results listed in Table 5 show that high density black dye transfer images can be made with dye-donor elements incorporating a dye mixture containing a cyan dye of the present invention.

Example 8 The melting points of the corresponding pyruvamide dyes C3 and C4 and their solubilities at room temperature in ecologically acceptable solvents such as 2-butanone are shown in Table 6.

[0073]

[Table 13]

From Table 6, the dyes of the invention have a high solubility in ecologically acceptable organic solvents such as 2-butanone and have a lower melting point than the corresponding pyruvamide dyes (C3 vs. 2; C4 vs. 30). Due to the low solubility of the pyruvamide dyes C3 and C4, they crystallize in the dye-donor element, especially when large amounts of dye are used in the donor sheet to obtain high concentrations.

Claims (6)

[Claims] 1. A dye-donor element for use in dye sublimation thermal transfer, comprising a support provided with a dye layer containing a dye and a polymeric binder; said dye having the formula (I): [Wherein R ¹ , R ² and R ³ are each independently hydrogen,
Halogen, nitro, alkyl group, cycloalkyl group, aryl group, allyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, amino group, CN, carboalkoxy group, sulfonylamino group or carbonamido group. Represents any of these groups, or R ² and R ³ represent the atoms necessary to form a ring with the atom to which they are connected; R ⁴ represents OR ⁵ , SR ⁵ , NR ⁵ R
⁶ or a heterocyclic ring (wherein R ⁵ and R ⁶ each independently represent hydrogen, an alkyl group, an allyl group, an aryl group, a cycloalkyl group, an alkenyl group or a heterocyclic ring, or R ⁵ and R ⁶ R ⁶ represents the atom necessary to form a heterocyclic ring with the atoms to which they are attached; R ⁷ and R ⁸ each independently represent hydrogen, an alkyl group, an aryl group or a heterocyclic group. , Or R ⁷ and R ⁸ represent the atoms necessary to form a heterocyclic ring with the atoms to which they are connected, or R ⁷ or R ⁸ and R ⁹ or R ¹² are the atoms to which they are connected. Represents the atoms necessary to form a ring with R
⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently hydrogen, hydroxy, halogen, alkyl group, cycloalkyl group, aryl group, amino group, alkyloxy group, aryloxy group, carbamoyl group, sulfamoyl group, NH -SO
_{^{2 R 13, NH-COR 13}} , O-SO 2 R 13 or O-
Represents COR ¹³ , and R ⁹ and R ¹⁰ or R ¹¹ and R ¹² represent an atom necessary for forming a ring together with the atom to which they are connected (in the formula, R ¹³ is an alkyl group, a cycloalkyl group, Alkenyl group, aralkyl group, aryl group, alkyloxy group, aryloxy group, alkylthio group,
Represents an arylthio group, amino group or heterocyclic group)]
A dye-donor element represented by: 2. The dye-donor element according to claim 1, further comprising a yellow and magenta dye which renders the dye layer black. 3. A dye of formula (I) as defined in claim 1. 4. A dye layer of a dye-donor element as defined in claim 1 or 2 is placed in face-to-face relationship with a dye image-receiving layer of a receiving sheet; the combination thus obtained. Is heated in the image forming direction; then the receiving sheet is separated from the dye-donor element; and the image is formed by the dye sublimation thermal transfer process. 5. A combination comprising (i) a dye-donor element having a dye layer containing a dye and a polymer binder on a support, and (ii) a receiving sheet used in combination with the dye-donor element. A combination characterized in that said dye is a dye as defined in claim 1. 6. The combination of claim 5 wherein said dye receiving material further comprises in said dye layer a yellow and magenta dye which renders said dye layer black.